DE2122956A1 - Process for the production of liquid butadiene polymers - Google Patents

Description

Verfa hre polymers for Prod RECOVERY · f s lüssig Buta diene n

The invention relates to a process for the production of liquid butadiene polymers with predominantly central double bonds and viscosities between 50 and 50,000 cP (20 ^° C.) in the presence of mixed catalysts made from nickel compounds and organoaluminum compounds which are soluble in inert solvents.

It is known that liquid polybutadienes or liquid butadiene copolymers can be prepared by polymerizing butadiene or copolymerizing butadiene with other di- or monoolefins in the presence of mixed catalysts from nickel compounds soluble in inert solvents and organoaluminum compounds and in the presence of inert diluents. In these production processes, the polymerization is generally carried out at temperatures of up to 30.degree. The space-time yield is essentially limited by the maximum amount of heat that can be dissipated. For a polymerization on a technical scale, it is therefore advantageous if the highly exothermic polymerization reaction can take place at temperatures above 30 ⁰ C. This allows the temperature difference between the reactor contents and the cooling medium to be

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large and the released heat of reaction can be dissipated faster. This leads to higher space-time yields, which is of great importance for the economy of a process. However, as the polymerization temperature rises, the viscosity of the polymers prepared under the above-mentioned conditions increases. This increase in viscosity cannot be compensated for by the regulators known hitherto for the production of liquid butadiene polymers, such as, for example, amines or vinylcycloolefins, without a simultaneous strong reduction in yield. These controls can not be added in any amount jeäer the reaction mixture, excluding the catalyst sy stem .bieren inhi-to. Likewise, when using these regulators, it is not possible to carry out the polymerization with a higher butadiene concentration in a solvent or even without a solvent, without the viscosity of the product obtained increasing very sharply or the batch gelling.

The present invention therefore has the task of overcoming these disadvantages of the prior art in a simple manner.

This object was achieved in that the liquid butadiene polymers in the presence of unsaturated hydrocarbons of the general formula

R ₁ - CH =

in the R. and R- hydrogen, chlorine or alkyl radicals with 1 to

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5 carbon atoms and R_ denote hydrogen or chlorine and polymerized x ^ earth at temperatures of 10 to 180 C with the exclusion of oxygen and moisture. Preferably such unsaturated hydrocarbons are used, in which R. and R.sup.1 denote alkyl radicals with 1 to 2 carbon atoms.

In the context of the present invention, butadiene polymers are understood as meaning homopolymers and copolymers of butadiene. Λ Suitable comonomers for the production of butadiene copolymers are, for example, those diolefins which contain more than 4 carbon atoms, styrene and substituted styrenes. Isoprene, 2,3-dimethylbutadiene, styrene oroC-methylstyrene can preferably be used in the copolymerization.

The mixed catalysts suitable for the process according to the invention order once from nickel compounds that are soluble in the diluents used. As such, nickel compounds to be mentioned are nickel salts such as nickel octoate and nickel oleate and nickel complexes such as nickel acetylacetonate. Nicke 1-tetracarbonyl, Ni / QZ-bis-cyclooctadiene, diallyl nickel or Dicyclopentadienyl nickel. ™

The nickel is in the form of the compound in amounts of 0.0005 to 0.5 parts by weight, based on the amount of or the Monomers used in the polymerization.

On the other hand, the mixed catalysts contain aluminum compounds the general formula

^R n ^A1X 3-n

in which R is hydrogen, an alkyl, aryl or alkylaryl radical

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with 1 to 3 carbon atoms, X is chlorine or bromine and η is a number between 1 and 2. Ethyl aluminum sesquichloride, Al (C ₂ H ₅ ) ^ ₅ Cl _{1 5} is preferably used.

The aluminum compound is used in the polymerization in such concentrations that the amount of aluminum is 0.01 to 2, preferably 0.05 to 1, parts by weight, based on the amount of the monomer (s).

The molar ratio of the Ni to the Al compound is generally 1 ί 4 to 1: 100, preferably 1: 4 to 1 ί 50.

Suitable unsaturated hydrocarbons due to the fact that they are mixed with the aforementioned mixed catalysts are not or only hardly polymerizable, can be used as regulators, are e.g. ethylene, propylene, n-butene- (1), n ~ butene- (2), unbranched pentenes, hexenes, octenes, vinyl chloride and vinylidene chloride.

Surprisingly, these unsaturated hydrocarbons have the property, in comparison with the regulators known hitherto for the production of liquid butadiene polymers, that they regulate more strongly at higher temperatures than at lower ones. In the process according to the invention, too, the viscosity of the end product increases from a given polymerization temperature with increasing temperature, but not to the same extent as, for example, when regulating with amines (see Table 1).

A particular advantage of the method according to the invention is it that the regulating unsaturated hydrocarbons can also be used in larger concentrations, without

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id · '; lead to an inhibition of the catalyst system.

The regulating effect of the claimed unsaturated hydrocarbons differs from substance to substance, but it increases for each substance with increasing concentration in the polymerization batch. The property of the unsaturated hydrocarbons also allows them to be used alone or in a mixture as a diluent in the polymerization. Propylene, butene-1 and butene-2 are particularly suitable for this purpose. Consequently, butadiene-containing C. cuts, in which the butadiene is present as a monomer and the butenes are present as a diluent in addition to butanes, can also be used directly in the polymerization. The butadiene content of the C. cuts should be 20 to 90 %, preferably 30 to 80 % .

The use of propylene or butenes also offers the advantage that the heat released during the polymerization in particular in the case of a continuous procedure - can be removed in a simple manner by evaporative cooling.

Correspondingly, it is also possible when using the somewhat more strongly regulating ethylene without an additional solvent, butadiene to polymerize practically in bulk, the heat of polymerization also being dissipated by evaporative cooling can be.

In the process according to the invention it is also possible that, in addition to the unsaturated hydrocarbons, also known ones Regulators are added if particular advantages are achieved by this combination.

In the process according to the invention, diluents can be used except for the unsaturated hydrocarbons already mentioned

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XU · '::

substances from the series of aliphatic and aromatic hydrocarbons are used. Butane, hexane, cyclohexane, benzene, toluene and xylene are preferred used.

The polymerization takes place at temperatures between 10 and 180 ^° C., preferably between 30 and 125 ^° C., with exclusion of oxygen and moisture, at autogenous pressure, optionally under an inert gas atmosphere.

The inventive method can both continuously as can also be carried out discontinuously.

The polymer solutions obtained are worked up in a manner known per se, for example by decomposing the mixed catalyst with water, to which inorganic or organic bases or acids can optionally be added and which is ^{heated to above 50 °} C., and at the same time the organic phase is washed with it. After the washing water has been separated off, the diluent is distilled off from the polymer.

The liquid butadiene polymers obtained have, depending on the reaction conditions chosen for the preparation, average molecular weights from 500 to 10,000, preferably from 750 to 5,000, and viscosities from 50 to 50,000 centipoise, preferably from 150 to 10,000 centipoise, at 20 ° C. in a Hoepler Falling ball viscometer measured according to Haake. The liquid butadiene polymers produced by the claimed process have 30 to 90 %, but mostly 60 to 85 % cis double bonds, 10 to 70 %, but mostly 15 to 40 %, trans double bonds and less than 5 % vinyl double bonds.

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The liquid produced by the process according to the invention Butadiene polymers are suitable for many technical purposes, e.g. as a plasticizer for rubbers, for the production of air-drying coatings, as starting materials for secondary products v.'ie maleic anhydride or fumaric acid adducts, which in saponified form are water soluble and are epoxies.

The following are used to further explain the invention

Examples. (|

Example 1 (experiments 1-10) and comparative example (experiments A-H)

100 parts by weight of dry benzene and 10 parts by weight of butadiene are placed in a pressure reactor under a nitrogen atmosphere. Subsequently, 0.06 part by weight of Ni as nickel octoate, 0.9 parts by weight of ethylenium sesquichloride in the form of a 20% benzene solution and - as in experiment A - the amount of regulator specified in Table 1 are added with stirring. At the reaction temperature also shown in Table 1, 90 parts by weight of butadiene are then added over the course of 2 to 4 hours. The mixture is left for half an hour and then washes the nachrtihren React ion solution with 300 parts by weight TEI len% hydrochloric acid water of pH 2. After separation of the aqueous solution is distilled benzene from the oily polymers.

The conversions achieved and the viscosities of the butadiene polymers can be found in Table 1.

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Tabel 1 Temp. 2 Regulator • sales viscosity ⁰ C Amount of regulator % cP / 2O ⁰ C attempt 10 Xethylene related to butadiene 96 1100 25th It 1.0 97 752 1 25th Il 1.0 96 300 2 25th Il 5.0 98 210 3 30th Il 7.5 90 . 160 4th 40 •1 10.0 95 665 5 40 N 1.0 85 99 6th 50 Il 15.0 98 1031 7th 100 Il ι, ο 99 29700 * 8th loo H 1.0 96 905 9 25th - 7.5 100 2315 10 10 NH ₃ _ 100 715 A. 25th Il 0.03 95 730 B. 25th M. 0.03 - - C. 40 ti 0.3 95 1070 D. 50 Il 0.03 96 4390 E. 100 η 0.03 98 retaliate P. 100 Il 0.03 <1O not best. 6th 0.3 H example

In e _(INEM pressure reactor given in Table 2. amounts of solvent and / or amounts indicated regulator together with 5 parts by weight of butadiene are charged under a nitrogen atmosphere. Subsequently, the amounts given also in Table Xthylalurainiumseaguichlorid and Ni are added as Ni octoate and thereafter 95 parts by weight of butadiene were still 95 parts by weight within 2.5 hours at the temperature indicated in the table.

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Tabel

attempt

solvent

Art

Regulator

Wt. ~ T. Art

Weight -T.

Ni

Weight -T.

1.5 ⁰¹ I, 5

Parts by weight

Sales viscosity

eP / 20

O (O CO

. 1 2

·. 3 4 5 6

'7

. 8 9

10

benzene

Il Il Il Il Il Il Il Il

Hexane

20th Ethylene 8th ίο Il 8th 5 Il 8th - Il 8th 70 Propylene 30th 70 Il 30th 70 Il 30th 70 Il 30th 70 Il 30th 100 Xthvlen 10

0.01 0.01

0.01

0.01

0.025

0.025

0.025

0.025

0.025

0.025

0.2
0.2
0.2
0.2
0.5
0.5
0.5
0.5
0.5
0.5

45

45

45

45

45

60

100

125

150

45

92 92 95 92 100 93 90 75 60 92

233

285 519 579 525 567

1290 990

3440 246

N) N> CO

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-t.

Example 3

In a pressure reactor, 300 parts by weight of a C - hydrocarbon mixture, the composition of which is from Table 3b can be seen, if necessary together with an additional regulator, the type and amount of which can also be found in the table 3a can be seen. Then initially 0.04 wt% nickel as nickel octoate and then 0.9 wt% ethyl aluminum sesquichloride (based on the butadiene contained in the C. hydrocarbon mixture). The reaction batch is held for 3 hours at the temperature given in Table 3a, then by adding 600 parts by weight of hydrochloric acid Water stopped and washed and worked up in the manner described.

The conversions achieved and the viscosities of the butadiene polymers of the experiments can be found in Table 3a.

. €: ■ <

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Table 3a

Attempt temp. Solvent

additional regulator

Art

% By weight or
on butadiene

Turnover %

Viscosity cP / 20

1 25th butane 2 25th η-butene- (I) 3 25th n-butene- (2) 4th 25th C ^ -KW mixture 5 25th Il 6th 40 Il • n
I. 25th Il 8th 25th Il ■ 9 25th ti

Ethylene

Il

NH ₃

Vinyl chloride

Vinylidene chloride

- 68 not measurable - 99 1500 - 100 1500 - 95 2358 1.0 94 1125 5.0 89 860 0.04 64 880 2.5 85 . 870 5.0 89 889

to cn cn

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Table 3b

Composition of the C. hydrocarbon mixtures (% by weight)

Attempt 1 Attempt 2 Attempt 3 Trial 4 to 9 Butadiene (1.3) 40.2 41.12 41.2 41.13 Butadiene- (1,2) m 0.01 0.01 0.02 0.01 η-butene- (1) 0.08 58.53 0.13 15.37 η-butene (2) ice 0.09 0.07 22.84 4.65 η-butene- (2) -tr. 0.09 0.01 32.0 5.44 i-butene 0.1 0.01 0.05 28.04 n-butane 59.24 0.26 0.06 4.53 i-butane 0.11 '0.01 3.45 0.82 Butyne- (1) 0.01 0.01 0.01 0.01 Butyne- (2) 0.01 0.01 0.01 0.01 Vinyl acetylene 0.02 0.01 0.01 0.01

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Claims (1)

Process for the production of liquid butadiene polymers with predominantly intermediate double bonds and viscosities between 50 and 50,000 cP (20 ⁰ C) in the presence of mixed catalysts composed of nickel compounds soluble in inert solvents and organoaluminum compounds, characterized in that the liquid butadiene polymers in the presence of unsaturated a Hydrocarbons of the general formula Rr \\ J - / "· in which R. and R_ denote hydrogen, chlorine or alkyl radicals with 1 to 5 carbon atoms and R denotes hydrogen or chlorine, ^{are polymerized at temperatures from 10 to 180 °} C. with exclusion of oxygen and moisture. 2. The method according to claim 1, characterized in that polymerized at temperatures of 30 to 125 C. 3. The method according to claims 1 and 2, characterized in that ^ -hydrocarbon mixtures rait butadiene contents from 30 to 80% are used in the polymerization. 4. The method according to claims 1 to 3, characterized in that ethylene, propylene, butene (1) and / or butene (2) as unsaturated Hydrocarbons are used. 209849/0924 - 14 -. O.g. 2543 6.5.1971 κί- ~ 5. The method according to claims 1 to 4, characterized in that additionally polymerized in the presence of other inert diluents such as butane, cyclohexane, benzene, toluene, xylene will. 6. The method according to claims 1 to 5, characterized in that in addition to the unsaturated hydrocarbons, additional regulators how ammonia or amines are used. // la 209849/0924